Copolymerizable, ultraviolet light absorber 4-allyloxybenzal-1-phenylhydrazones

ABSTRACT

This invention relates to copolymerizable ultraviolet light absorber compounds having the formula: ##STR1## where R is alkylene, C 1  -C 10 , hydroxyalkylene, C 1  -C 10 , alkylene-oxyalkylene, C 1  -C 10  or phenylene, C 1  -C 10 , unsubstituted or substituted with hydroxy; 
     R&#39; and R&#34; are independently hydrogen or akyl; C 1  -C 6  ; and R&#34;&#39; is hydrogen or akyl, C 1  -C 6 .

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to novel copolymerizable ultraviolet lightabsorber compounds, and, more particularly, to4-allyloxybenzal-1'-alkyl-1'-phenylhydrazone compounds which arecopolymerizable with vinyl monomers to provide polymer materials havingimproved resistance to degradation to light.

2. Description of the Prior Art

Various organic compounds exhibit the power to absorb electromagneticradiation and can be incorporated in various plastic materials such astransparent sheets which act as filters for all the radiation passingthrough and will transmit only such radiations as are not absorbed bythe sheet and/or the absorbing agent. Such filters find use in manytechnical and commercial applications.

Numerous cyano acrylic compounds have been suggested as absorbents forthe range of radiations described above. For specific compounds, seeU.S. Pat. Nos. 3,081,280; 3,272,810; 3,644,466; 3,256,312; and3,215,724. These ultraviolet absorbers are mechanically mixed with theplastic materials to prevent discoloration and degradation of thematerial. However, it has been observed that such absorbers sometimesfail or are blocked out of the plastic under adverse weather conditionsbefore the lifetime of the protected material. Also, it is not possibleto use all of these ultraviolet absorbers with radiation curing of theplastic material. Another disadvantage of these ultraviolet absorbers isthe high amount of absorber needed for protection of some materials.

Among the other uses of copolymerizable absorbers is in skin care andhair care compositions, but these generally require materials whichabsorb at relatively longer wavelengths than previously available.

Accordingly, it is an object of the present invention to provide novelcopolymerizable ultraviolet light absorber compounds which aresubstantially free of the disadvantages of the prior art.

Another object of this invention is to provide novel compounds which canbe copolymerized directly with monomers, such as plastic material, toprovide more permanent ultraviolet light protection.

Still another object is to provide copolymerizable monomers which absorbat wavelengths suitable for skin and hair care compositions.

A specific object is to provide ultraviolet light absorber compoundscontaining a copolymerizable ethylenic group.

These and other objects and features of the invention will be madeapparent from the following more particular description of theinvention.

SUMMARY OF THE INVENTION

What is provided herein are improved, novel copolymerizable ultravioletlight absorber compounds of the formula: ##STR2## where R is alkylene,C₁ -C₁₀, hydroxyalkylene, C₁ -C₁₀, alkylene-oxyalkylene, C₁ -C₁₀ orphenylene, C₁ -C₁₀, unsubstituted or substituted with hydroxy.

R' and R" are independently hydrogen or alkyl, C₁ -C₆, and

R"' is hydrogen or alkyl, C₁ -C₆.

In the best mode of the invention, R is alkylene, --CH₂ --, R' and R"are both hydrogen, and R"' is --CH₃.

DETAILED DESCRIPTION OF THE INVENTION

The compounds of the invention contain ultraviolet light absorber andcopolymerizable portions in the same molecule. These portions areeffectively separated so that each can perform its own function withoutinterference from the other. Therefore, the absorber portion does notinhibit the copolymerization, and the ethylenic radical does not effectthe light absorbing properties of the molecule.

The --RCR'═CHR" radical is copolymerizable with vinyl monomers so thatthe ultraviolet absorber an integral part of the polymer. Suitableradicals are allyl, crotyl, methylpropenyl, vinylbenzyl, vinyloxyethyl,allyloxy-2-hydroxypropyl, and 2-hydroxy-3-butenyl. The best mode isrepresented by allyl. The novel compounds of the invention may beprepared, e.g. from 4-hydroxybenzal-1'-alkyl-1'-phenylhydrazone byalkylation with an ethylenic halide.

The novel compounds of this invention are colorless solids which areinsoluble in water. The benzal alkylphenylhydrazone chromophore of thecompounds herein has an ultraviolet absorbance peak at about 340 nm, butno visible absorbance. The compounds of the invention absorb in the330-400 nm range, which is particularly suitable for skin and hair carecompositions.

The flow sheet below illustrates the reaction sequence for preparing thecompounds of the invention. ##STR3## where Z is a halide and R', R" andR"' are as defined above.

Representative --RCR'--CHR" radicals are --CH₂ --CH═CH₂ (allyl), --CH₂CH═CHCH₃ (crotyl), ##STR4##

The alkylation of the phenol is carried out with a reactive ethyleniccompound, such as an ethylenic halide, e.g. allyl chloride or allylbromide. The reaction is carried out in an inert solvent, such asacetone, at a suitable temperature, generally at the reflux temperatureof the solvent, for about 24 hours. The reactants are controlled toprovide at least a 1:1 molar ratio of the ethylenic halide to the phenolcompound.

The compounds of the invention may be copolymerized, for example, withmonomers and oligomers by conventional free radical polymerization orwith radiation curing, if desired, to provide useful polymeric coatings,or formulated into cosmetic preparations, such as skin and hair careproducts.

The following examples will describe the invention with moreparticularity.

EXAMPLE 1 4-Allyloxybenzal-1'-Methyl-1'-Phenylhydrazone ##STR5## A.4-Hydroxybenzal-1'-Methyl-1'-Phenylhydrazone

To 50 ml of ethanol having dissolved therein 12.5 gp-hydroxybenzaldehyde (0.1 mole) is added 12.5 g (0.1 mole) of1-methyl-1-phenylhydrazine. The mixture is heated at reflux for 1 hourand cooled. Then water is added until the solution becomes cloudy. Thesolid that separates is filtered giving 22 g (95%) of crude material.Recrystallization from methanol/water gives product; nmr (chloroform)has singlet at δ=33 (3 protons) and complex multiplet centered at δ=7.2(10 protons).

B. 4-Allyloxybenzal-1'-Methyl-1'-Phenylhydrazone

In a flask with magnetic stirrer and reflux condenser is dissolved 4.4 g(0.02 moles) of 4-hydroxybenzal-1'-methyl-1'-phenylhydrazone in 50 mlacetone. To this is added 2.4 g allyl bromide and 2.8 g K₂ CO₃. Thereaction mixture is heated to reflux for 4 hrs. 15 min., and thencooled. The solids are filtered off; then the solvent evaporated. Thesolid residue is stirred for 1 hr in 50 ml of 5% NaOH solution thenfiltered and air dried giving 4 g (77.2%) tan product; nmr (chloroform)has singlet at δ=3.4 (3 protons), doublet at δ=4.5 (2 protons), complexmultiplet centered at δ=5.4 (3 protons), and complex multiplet centeredat δ=7.2 (10 protons).

EXAMPLE 2 4-Crotyloxybenzal-1'-Methyl-1'-Phenylhydrazone ##STR6##

When crotyl bromide was substituted for allyl bromide in Example 1, thedesired product is obtained.

EXAMPLE 3 4-(2-Methylpropenyloxy)benzal-1'-Methyl-1'-Phenylhydrazone##STR7##

When 3-chloro-2-methyl-1-propene was substituted for allyl bromide inExample 1, the desired product is obtained.

EXAMPLE 4 4-(4-Vinylbenzyloxy)benzal-1'-Methyl-1'-Phenylhydrazone##STR8##

When vinylbenzyl chloride was substituted for allyl bromide in Example1, the desired product is obtained.

EXAMPLE 5 4-(Vinyloxyethyloxy)benzal-1'-Methyl-1'-Phenylhydrazone##STR9##

When vinyloxyethyl chloride was substituted for allyl bromide in Example1, the desired product is obtained.

EXAMPLE 64-(3-Allyloxy-2-Hydroxypropyloxy)benzal-1'-Methyl-1'-Phenylhydrazone##STR10##

When 0.1 moles of the phenol of Example 1 and allyl glycidyl ether, and,250 mg. of tetramethylammonium chloride are heated at 150° C. for 16hrs., diluted with 50 ml. methylene chloride, decolorized, filtered, andevaporated the desired product is obtained.

EXAMPLE 7 4-(2-Hydroxy-3-Butenyloxy)benzal-1'-Methyl-1'-Phenylhydrazone##STR11##

When 2-hydroxy-3-butenyl bromide was substituted for allyl bromide inExample 1, the desired product was obtained.

EXAMPLE 8

The monomer compound of Example 1 is copolymerized with another monomerby charging a flask with 150 ml ethanol, 1.5 g4-allyloxybenzal-1'-methyl-1'-phenylhydrazone and 50 g vinylpyrrolidone. The contents are heated to 75° C. under N₂ andpolymerization is initiated with 0.2 g azobis-isobutyronitrile (AIBN).After 1.5 hrs., another 0.2 g AIBN is added and heating is continued foranother 1.5 hrs. The solvent is concentrated and added to stirred ether.A white precipitate of the copolymer is obtained which is filtered anddried, giving 18 g (36%) of product. A 5% aqueous solution of thecopolymer is filtered; the ultraviolet spectra of the filtrate showsthat the copolymer contains 5.8% of the absorber compound.

While certain preferred embodiments of the present invention have beenillustrated by way of specific example it is to be understood that thepresent invention is in no way to be deemed as limited thereto butshould be construed as broadly as all or any equivalents thereof.

What is claimed is:
 1. Copolymerizable ultraviolet light absorbercompounds having the formula: ##STR12## where R is alkylene, C₁ -C₁₀,hydroxyalkylene, C₁ -C₁₀ alkyleneoxyalkylene, C₁ -C₁₀, phenylene, C₁-C₁₀, unsubstituted or substituted with hydroxy;R' and R" areindependently hydrogen or alkyl, C₁ -C₆ ; and; R"' is hydrogen or alkylC₁ -C₆.
 2. Compounds according to claim 1 in which R"' is methyl. 3.Compounds according to claim 1 in which --RCR'═CHR" is allyl, crotyl,methylpropenyl, vinylbenzyl, vinyloxyethyl, allyloxy-2-hydroxypropyl, or2-hydroxy-3-butenyl.
 4. A compound according to claim 1 which is4-allyloxybenzal-1'-methyl-1'-phenylhydrazone.
 5. A compound accordingto claim 1 which is 4-crotyloxybenzyl-1-methyl-1'-phenylhydrazone.
 6. Acompound according to claim 1 which is4-(4-vinylbenzyloxy)benzal-1'-methyl-1'-phenylhydrazone.
 7. A compoundaccording to claim 1 which is4-(2-methylpropenyl)oxybenzal-1'-methyl-1'-phenylhydrazone.
 8. Acompound according to claim 1 which is4-(vinyloxyethyl)oxybenzal-1'-methyl-1'-phenylhydrazone.
 9. A compoundaccording to claim 1 which is4-(3-allyloxy-2-hydroxypropyloxy)benzal-1'-methyl-1'-phenylhydrazone.10. A compound according to claim 1 which is4-(2'-hydroxy-3-butenyloxy)benzal-1'-methyl-1'-phenylhydrazone.